Process for producing phenylene-containing polymer and film-forming material

ABSTRACT

The present invention is a process for producing a phenylene-containing polymer in the presence of a catalyst system containing a transition metal compound, and a film-forming material comprising the phenylene-containing polymer.

TECHNICAL FIELD

This invention relates to an organic solvent-solublephenylene-containing polymer which has high heat resistance, lowdielectric properties, and excellent processability.

BACKGROUND ART

Reflecting the advancement of fine processing technology, large scaleintegration (LSI) has ever been increasing in integration, function, andperformance. As a result, the circuit resistance and condensercapacitance between interconnection lines (called parasitic resistanceand parasitic capacitance, respectively) increase to increase not onlypower consumption but retardation time, which is a great cause ofreduction of signal speed of a device.

It has therefore been demanded to reduce parasitic resistance orparasitic capacitance. One of the solutions is to cover the peripheriesof interconnection lines with an interlayer dielectric film to reducethe parasitic capacitance so as to cope with speeding up of devices. Inthis case, the interlayer dielectric film must have excellent heatresistance withstanding a thin film formation step for producing amounting substrate or post steps, such as chip bonding and pin insertionmounting.

Polyimide is widespread as a highly heat-resistant organic material forthis use but, containing a highly polar imido group, unsatisfactory fromthe standpoint of low dielectric properties and low water absorbability.

On the other hand, polyphenylene is known as a heat-resistant organicmaterial containing no polar group. Because polyphenylene is, whileexcellent in heat resistance, inferior in solubility in organicsolvents, it is a practice generally followed to introduce a side chain.Polyphenylene having a side chain includes polymers described in U.S.Pat. No. 5,214,044, WO 96/28491, and EP 629217.

These polymers have a basic structure mainly comprising apoly-p-phenylene structure and, in some cases, a flexible monomer unit.They are soluble only in specific organic solvents and have poorprocessability. Besides, many of them carry a polar group or an alkylgroup as a side chain and therefore fail to fully satisfy therequirements of heat resistance and low dielectric properties.

Further, most of these conventional polymers are produced by startingwith aromatic dichloro compounds such as p-dichlorobenzene derivatives.When a fluoroalkyl group or an aryl group is to be introduced as a sidechain in an attempt to obtain a heat-resistant low-dielectric materialfrom such an aromatic dichloro compound, there are accompanyingdisadvantages, such that the synthesis of the monomer becomescomplicated, the monomer cannot be secured in a stable manner, and thedegree of polymerization does not rise sufficiently on account of thesteric hindrance of the side chain.

Thus there has been found no polyphenylene that could fulfill therequirements of heat resistance, low dielectric properties andprocessability and that could be produced economically.

DISCLOSURE OF THE INVENTION

An object of the present invention is to overcome the above-mentionedproblems and to provide a soluble resin excellent in heat resistance,low dielectric properties, processability and transparency.

The present invention provides a process for producing aphenylene-containing polymer comprising polymerizing a monomercomprising not less than 50 mol % of a compound represented by formula(I):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; R¹, R², R³,R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; and Z represents an alkylgroup, a halogenated alkyl group or an aryl group,

in the presence of a catalyst system containing a transition metalcompound.

BRIEF DESCRIPTION OF THE DRAWINGS

FIGS. 1 to 20 each show the IR spectrum of the polymers obtained inExamples 1 to 20.

BEST MODE FOR PRACTICING INVENTION

Of the groups represented by Y or Y′ in formula (I), the halogenatedalkyl group includes a trifluoromethyl group and a pentafluoroethylgroup; and the aryl group includes a phenyl group, a tolyl group, and apentafluorophenyl group.

Of the groups and atoms represented by R¹, R², R³, R⁴, R⁵, R⁶, R⁷, andR⁸ in formula (I), the halogen atom includes a fluorine atom; the alkylgroup include a methyl group and an ethyl group; the halogenated alkylgroup includes a trifluoromethyl group and a pentafluoroethyl group; theallyl group includes a propenyl group; and the aryl group includes aphenyl group.

Of the groups represented by Z in —OSO₂Z in formula (I), the alkyl groupincludes a methyl group and an ethyl group; the halogenated alkyl groupincludes a trifluoromethyl group; and the aryl group includes a phenylgroup, a p-fluorophenyl group, and a p-tolyl group.

X in formula (I) is preferably a group of formula:

—C(CF₃)₂—, a group of formula:

or a fluorenylene group of formula:

with the fluorenylene group being preferred.

Examples of the phenylene-containing compounds represented by formula(I) are 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane,bis(4-methylsulfonyloxyphenyl)methane,bis(4-methylsulfonyloxyphenyl)diphenylmethane,2,2-bis(4-methylsulfonyloxy-3-methylphenyl)hexafluoropropoane,2,2-bis(4-methylsulfonyloxy-3-propenylphenyl) hexafluoropropane,2,2-bis(4-methylsulfonyloxy-3,5-dimethylphenyl)hexafluoropropane,9,9-bis(4-methylsulfonyloxyphenyl)fluorene,9,9-bis(4-methylsulfonyloxy-3-methylphenyl)fluorene,9,9-bis(4-methylsulfonyloxy-3,5-dimethylphenyl)fluorene,9,9-bis(4-methylsulfonyloxy-3-propenylphenyl)fluorene,9,9-bis(4-methylsulfonyloxy-3-phenylphenyl)fluorene,bis(4-methylsulfonyloxy-3-methylphenyl)diphenylmethane,bis(4-methylsulfonyloxy-3,5-dimethylphenyl)diphenylmethane,bis(4-methylsulfonyloxy-3-propenylphenyl)diphenylmethane,bis(4-methylsulfonyloxy-3-fluorophenyl)diphenylmethane,bis(4-methylsulfonyloxy-3,5-difluorophenyl)diphenylmethane,9,9-bis(4-methylsulfonyloxy-3-fluorophenyl)fluorene,9,9-bis(4-methylsulfonyloxy-3,5-difluorophenyl)fluorene,bis(4-methylsulfonyloxyphenyl)methane,bis(4-methylsulfonyloxy-3-methylphenyl)methane,bis(4-methylsulfonyloxy-3,5-dimethylphenyl)methane,bis(4-methylsulfonyloxy-3-propenylphenyl)methane,bis(4-methylsulfonyloxyphenyl)trifluoromethylphenylmethane,bis(4-methylsulfonyloxyphenyl)phenylmethane,2,2-bis(4-trifluoromethylsulfonyloxyphenyl)hexafluoropropane,bis(4-trifluoromethylsulfonyloxyphenyl)methane,bis(4-trifluoromethylsulfonyloxyphenyl)diphenylmethane,2,2-bis(4-trifluoromethylsulfonyloxy-3-methylphenyl)hexafluoropropane,2,2-bis(4-trifluoromethylsulfonyloxy-3-propenylphenyl)hexaflfuoropropane,2,2-bis(4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl)hexafluoropropane,9,9-bis(4-trifluoromethylsulfonyloxyphenyl)fluorene,9,9-bis(4-trifluoromethylsulfonyloxy-3-methylphenyl)fluorene,9,9-bis(4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl)fluorene,9,9-bis(4-trifluoromethylsulfonyloxy-3-propenylphenyl)fluorene,9,9-bis(4-trifluoromethylsulfonyloxy-3-phenylphenyl)fluorene,bis(4-trifluoromethylsulfonyloxy-3-methylphenyl)diphenylmethane,bis(4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl)diphenylmethane,bis(4-trifluoromethylsulfonyloxy-3-propenylphenyl)diphenylmethane,bis(4-trifluoromethylsulfonyloxy-3-fluorophenyl)diphenylmethane,bis(4-trifluoromethylsulfonyloxy-3,5-difluorophenyl)diphenylmethane,9,9-bis(4-trifluoromethylsulfonyloxy-3-fluorophenyl)fluorene,9,9-bis(4-trifluoromethylsulfonyloxy-3,5-difluorophenyl)fluorene,bis(4-trifluoromethylsulfonyloxyphenyl)methane,bis(4-trifluoromethylsulfonyloxy-3-methylphenyl)methane,bis(4-trifluoromethylsulfonyloxy-3,5-dimethylphenyl)methane,bis(4-trifluoromethylsulfonyloxy-3-propenylphenyl)methane,bis(4-trifluoromethylsulfonyloxyphenyl)trifluoromethyl-phenylmethane,bis(4-trifluoromethylsulfonyloxyphenyl),2,2-bis(4-phenylsulfonyloxyphenyl)hexafluoropropane,bis(4-phenylsulfonyloxyphenyl)methane,bis(4-phenylsulfonyloxyphenyl)diphenylmethane,2,2-bis(4-phenylsulfonyloxy-3-methylphenyl)hexafluoropropane,2,2-bis(4-phenylsulfonyloxy-3-propenylphenyl)hexafluoropropane,2,2-bis(4-phenylsulfonyloxy-3,5-dimethylphenyl)hexafluoropropane,9,9-bis(4-phenylsulfonyloxyphenyl)fluorene,9,9-bis(4-phenylsulfonyloxy-3-methylphenyl)fluorene,9,9-bis(4-phenylsulfonyloxy-3,5-dimethylphenyl)fluorene,9,9-bis(4-phenylsulfonyloxy-3-propenylphenyl)fluorene,9,9-bis(4-phenylsulfonyloxy-3-phenylphenyl)fluorene,bis(4-phenylsulfonyloxy-3-methylphenyl)diphenylmethane,bis(4-phenylsulfonyloxy-3,5-dimethylphenyl)diphenylmethane,bis(4-phenylsulfonyloxy-3-propenylphenyl)diphenylmethane,bis(4-phenylsulfonyloxy-3-fluorophenyl)diphenylmethane,bis(4-phenylsulfonyloxy-3,5-difluorophenyl)diphenylmethane,9,9-bis(4-phenylsulfonyloxy-3-fluorophenyl)fluorene,9,9-bis(4-phenylsulfonyloxy-3,5-difluorophenyl)fluorene,bis(4-phenylsulfonyloxyphenyl)methane,bis(4-phenylsulfonyloxy-3-methylphenyl)methane,bis(4-phenylsulfonyloxy-3,5-dimethylphenyl)methane,bis(4-phenylsulfonyloxy-3-propenylphenyl)methane,bis(4-phenylsulfonyloxyphenyl)trifluoromethylphenylmethane,bis(4-phenylsulfonyloxyphenyl)phenylmethane,2,2-bis(-p-tolylsulfonyloxyphenyl)hexafluoropropoane,bis(p-tolylsulfonyloxyphenyl)methane,bis(p-tolylsulfonyloxyphenyl)diphenylmethane,2,2-bis(p-tolylsulfonyloxy-3-methylphenyl)hexafluoropropane,2,2-bis(p-tolylsulfonyloxy-3-propenylphenyl)hexafluoropropane,2,2-bis(p-tolylsulfonyloxy-3,5-dimethylphenyl)hexafluoropropane,9,9-bis(p-tolylsulfonyloxyphenyl)fluorene,9,9-bis(p-tolylsulfonyloxy-3-methylphenyl)fluorene,9,9-bis(p-tolylsulfonyloxy-3,5-dimethylphenyl)fluorene,9,9-bis(p-tolylsulfonyloxy-3-propenylphenyl)fluorene,9,9-bis(p-tolylsulfonyloxy-3-phenylphenyl)fluorene,bis(p-tolylsulfonyloxy-3-methylphenyl)diphenylmethane,bis(p-tolylsulfonyloxy-3,5-dimethylphenyl)diphenylmethane,bis(p-tolylsulfonyloxy-3-propenylphenyl)diphenylmethane,bis(p-tolylsulfonyloxy-3-fluorophenyl)diphenylmethane,bis(p-tolylsulfonyloxy-3,5-difluorophenyl)diphenylmethane,9,9-bis(p-tolylsulfonyloxy-3-fluorophenyl)fluorene,9,9-bis(p-tolylsufonyloxy-3,5-difluorophenyl)fluorene,bis(p-tolylsulfonyloxyphenyl)methane,bis(p-tolylsulfonyloxy-3-methylphenyl)methane,bis(p-tolylsulfonyloxy-3,5-dimethylphenyl)methane,bis(p-tolylsulfonyloxy-3-propenylphenyl)methane,bis(p-tolylsulfonyloxyphenyl)trifluoromethylphenylmethane, andbis(p-tolylsulfonyloxyphenyl)phenylmethane.

In the present invention, two or more compounds represented by formula(I) can be copolymerized.

The compound of formula (I) is synthesized by, for example, thefollowing process.

A bisphenol compound (e.g., 2,2-bis(4-hydroxyphenyl)hexafluoropropane)and two or more equivalents of a base are dissolved in a solvent.Pyridine can serve as both a base and a solvent. If desired, a catalystsuch as 4-dimethylaminopyridine can be added.

A sulfonic acid chloride (or anhydride) (e.g., methanesulfonic acidchloride) is added dropwise to the solution over a period of 5 to 60minutes in a dry nitrogen stream while maintaining the solution below15° C., followed by stirring at the same temperature for 0 to 60minutes. The stirring is continued at room temperature for 0 to 24 hoursto prepare a suspension. The resulting suspension is re-precipitated in3 to 20 times as much ice-water as the suspension. The precipitate iscollected and further purified by, for example, recrystallization togive bissulfonate compound crystals.

Alternatively a bisphenol compound (e.g.,2,2-bis(4-hydroxyphenyl)hexafluoropropane) is dissolved in 2 equivalentsof an alkali aqueous solution, such as a sodium hydroxide aqueoussolution. Separately, a sulfonic acid chloride (or anhydride) (e.g.,methanesulfonic acid chloride) is dissolved in an organic solvent, suchas toluene or chloroform. The two solutions are mixed and vigorouslystirred in the presence of, if desired, a phase transfer catalyst, suchas acetyltrimethylammonium chloride. The organic layer of the resultingreaction mixture is purified to yield a desired bissulfonate compound.

The compound of formula (I) can be copolymerized with at least onecompound selected from compounds represented by formulae (II) to (VI)shown below.

wherein R⁹, R¹⁰, R¹¹, and R¹², which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, a hydroxy group or amonovalent organic group; and R³¹ represents a halogen atom or a groupof formula: —OSO₂Z, wherein Z represents an alkyl group, a halogenatedalkyl group or an aryl group.

Of the groups represented by R³¹ in formula (II), the halogen atomincludes a chlorine atom, a bromine atom and an iodine atom.

Of the groups represented by Z in —OSO₂Z in formula (II), the alkylgroup includes a methyl group and an ethyl group; the halogenated alkylgroup includes a trifluoromethyl group; and the aryl group includes aphenyl group, a p-fluorophenyl group, and a p-tolyl group.

Of the atoms or groups as R⁹, R¹⁰, R¹¹, and R¹² in formula (II), thehalogen atom includes a fluorine atom, and the monovalent organic groupincludes an alkyl group, a halogenated alkyl group, an alkoxy group, anacetoxy group, a phenoxy group, and a benzoyl group. The organic groupis effective in improving the solubility of the resulting polymer. It ispreferred that R⁹, R¹⁰, R¹¹, and R¹² be a monovalent reactive group or aprecursor thereof, particularly be selected from the group consisting ofa hydroxyl group, a carboxyl group, an allyl group, and analkoxycarbonyloxy group. The reactive group precursor can be convertedto a corresponding reactive group through an appropriate treatmentfollowing polymerization. Introduction of the reactive group into thepolymer brings about improvements in solvent resistance and adhesion ofthe polymer.

Where adjacent two of R⁹, R¹⁰, R¹¹, and R¹² are each a carboxyl group,the two carboxyl groups can react to form an acid anhydride.

Examples of the compounds represented by formula (II) includep-dichlorobenzene, p-dibromobenzene, p-diiodobenzene,p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene, 2,5-dibromotoluene,2,5-diiodotoluene, 2,5-dimethylsulfonyloxybenzene,2,5-dichloro-p-xylene, 2,5-dibromo-p-xylene, 2,5-diiodo-p-xylene,2,5-dichlorobenzotrifluoride, 2,5-dibromobenzotrifluoride,2,5-diiodobenzotrifluoride, 1,4-dichloro-2,3,5,6-tetrafluorobenzene,1,4-dibromo-2,3,5,6-tetrafluorobenzene,1,4-diiodo-2,3,5,6-tetrafluorobenzene, 2,5-dichlorobenzoic acid,2,5-dibromobenzoic acid, methyl 2,5-dichlorobenzoate, methyl2,5-dibromobenzoate, t-butyl 2,5-dichlorobenzoate, t-butyl2,5-dibromobenzoate, and 3,6-dichlorophthalic acid anhydride.p-Dichlorobenzene, p-dimethylsulfonyloxybenzene, 2,5-dichlorotoluene,and 2,5-dichlorobenzotrifluoride are preferred.

wherein R⁹, R¹⁰, R¹¹, and R¹², which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, a hydroxy group or amonovalent organic group; and R³² represents a halogen atom or a groupof formula: —OSO₂Z, wherein Z represents an alkyl group, a halogenatedalkyl group or an aryl group.

Examples of the halogen atom and the monovalent organic group as R⁹,R¹⁰, R¹¹, and R¹² and the alkyl, halogenated alkyl or aryl group in R³²in formula (III) are the same as those enumerated as for formula (II).

To have at least one monovalent reactive group or reactive groupprecursor as R⁹, R¹⁰, R¹¹, and R¹² is preferred for improving theadhesion of the polymer.

Examples of the compounds represented by formula (III) arem-dichlorobenzene, m-dibromobenzene, m-diiodobenzene,m-dimethylsulfonyloxybenzene, 2,4-dichlorotoluene, 2,4-dibromotoluene,2,4-diiodotoluene, 3,5-dichlorotoluene, 3,5-dibromotoluene,3,5-diiodotoluene, 2,6-dichlorotoluene, 2,6-dibromotoluene,2,6-diiodotoluene, 3,5-dimethylsulfonyloxytoluene,2,6-dimethylsulfonyloxytoluene, 2,4-dichlorobenzotrifluoride,2,4-dibromobenzotrifluoride, 2,4-diiodobenzotrifluoride,3,5-dichlorobenzotrifluoride, 3,5-dibromotrifluoride,3,5-diiodobenzotrifluoride, 1,3-dibromo-2,4,5,6-tetrafluorobenzene,2,4-dichlorobenzyl alcohol, 3,5-dichlorobenzyl alcohol,2,4-dibromobenzyl alcohol, 3,5-dibromobenzyl alcohol,3,5-dichlorophenol, 3,5-dibromophenol,3,5-dichloro-t-butoxycarbonyloxyphenyl,3,5-dibromo-t-butoxycarbonyloxyphenyl, 2,4-dichlorobenzoic acid,3,5-dichlorobenzoic acid, 2,4-dibromobenzoic acid, 3,5-dibromobenzoicacid, methyl 2,4-dichlorobenzoate, methyl 3,5-dichlorobenzoate, methyl3,5-dibromobenzoate, methyl 2,4-dibromobenzoate, t-butyl2,4-dichlorobenzoate, t-butyl 3,5-dichlorobenzoate, t-butyl2,4-dibromobenzoate, and t-butyl 3,5-dibromobenzoate. Preferred of themare m-dichlorobenzene, 2,4-dichlorotoluene,3,5-dimethylsulfonyloxytoluene, and 2,4-dichlorobenzotrifluoride.

Apart from the compounds represented by formula (II) or (III),o-dichlorobenzene, o-dibromobenzene, o-diiodobenzene,o-dimethylsulfonyloxybenzene, 2,3-dichlorotoluene, 2,3-dibromotoluene,2,3-diiodotoluene, 3,4-dichlorotoluene, 3,4-dibromotoluene,3,4-diiodotoluene, 2,3-dimethylsulfonyloxybenzene,3,4-dimethylsulfonyloxybenzene, 3,4-dichlorobenzotrifluoride,3,4-dibromobenzotrifluoride, 3,4-diiodobenzotrifluoride,1,2-dibromo-3,4,5,6-tetrafluorobenzene, 4,5-dichlorophthalic acidanhydride, etc. can also be used as a copolymerizable monomer.

wherein R²¹ and R²², which may be the same or different, each representan alkyl group or an aryl group, provided that at least one of R²¹ andR²² is an alkyl group; R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, whichmay be the same or different, each represent a hydrogen atom, a halogenatom or a monovalent organic group; and R³³ represents a halogen atom ora group of formula: —OSO₂Z, wherein Z represents an alkyl group, ahalogenated alkyl group or an aryl group.

In formula (IV), the alkyl group as R²¹ or R²² includes a methyl group,an ethyl group, and a propyl group and the aryl group as R²¹ or R²²includes a phenyl group, a p-fluorophenyl group, and a p-tolyl group.

As for R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, the halogen atomincludes a fluorine atom; the monovalent organic group includes an alkylgroup, e.g., methyl, ethyl or propyl, a halogenated alkyl group, e.g.,trifluoromethyl or pentafluoroethyl, an aryl group, e.g., phenyl, and analkenyl group, e.g., propylenyl. As for Z, the alkyl group includes amethyl group, an ethyl group, and a propyl group; the halogenated alkylgroup includes a trifluoromethyl group and a pentafluoroethyl group; andthe aryl group includes a phenyl group, a p-fluorophenyl group, and ap-tolyl group.

Examples of the compounds represented by formula (IV) are2,2-bis(4-methylsulfonyloxyphenyl)propane,2,2-bis(4-methylsulfonyloxy-3-methylphenyl)propane,2,2-bis(4-methylsulfonyloxy-3-propenylphenyl)propane,2,2-bis(4-methylsulfonyloxy-3,5-dimethylphenyl)propane,2,2-bis(4-methylsulfonyloxy-3-fluorophenyl)propane,2,2-bis(4-methylsulfonyloxy-3,5-difluorophenyl)propane,2,2-bis(4-trifluoromethylsulfonyloxyphenyl)propane,2,2-bis(4-trifluoromethylsulfonyloxy-3-propenylphenyl)propane,2,2-bis(4-phenylsulfonyloxyphenyl)propane,2,2-bis(4-phenylsulfonyloxy-3-methylphenyl)propane,2,2-bis(4-phenylsulfonyloxy-3-propenylphenyl)propane,2,2-bis(4-phenylsulfonyloxy-3,5-dimethylphenyl)propane,2,2-bis(4-phenylsulfonyloxy-3-fluorophenyl)diphenylmethane,2,2-bis(p-tolylsulfonyloxyphenyl)propane,2,2-bis(p-tolylsulfonyloxy-3-methylphenyl)propane,2,2-bis(p-tolylsulfonyloxy-3-propenylphenyl)propane,2,2-bis(p-tolylsulfonyloxy-3,5-dimethylphenyl)propane,2,2-bis(p-tolylsulfonyloxy-3-methylphenyl)propane,2,2-bis(p-tolylsulfonyloxy-3,5-dimethylphenyl)propane,2,2-bis(p-tolylsulfonyloxy-3-propenylphenyl)propane,bis(p-tolylsulfonyloxy-3-fluorophenyl)propane,bis(p-tolylsulfonyloxy-3,5-difluorophenyl)propane, and1,1-bis(4-methylsulfonyloxyphenyl)-1-phenylethane.

wherein R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, which may be thesame or different, each represent a hydrogen atom, a halogen atom, analkyl group, a halogenated alkyl group or an aryl group; and R³⁴represents a halogen atom or a group of formula: —OSO₂Z, wherein Zrepresents an alkyl group, a halogenated alkyl group or an aryl group.

Examples of the compounds represented by formula (V) include4,4′-dimethylsulfonyloxybiphenyl, 4,4′-dibromobiphenyl,4,4′-diiodobiphenyl, 4,4′-dimethylsulfonyloxy-3,3′-dimethylbiphenyl,4,4′-dimethylsulfonyloxy-3,3,-difluorobiphenyl, and4,4′-dimethylsulfonyloxy-3,3′,5,5′-tetrafluorobiphenyl.

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ each represent ahydrogen atom or an allyl group, provided that at least one of R²³ toR³⁰ is an allyl group; and R³⁴ represents a halogen atom or a group offormula: —OSO₂Z, wherein Z represents an alkyl group, a halogenatedalkyl group or an aryl group.

Examples of the compounds represented by formula (VI) include4,4′-dimethylsulfonyloxy-3,3′-dipropenylbiphenyl, and3,3′-dipropenyl-4,4′-bis(4-fluorophenylsulfonyloxy)biphenyl.

In the compounds represented by formulae (V) and (VI), the group R³⁴ ispreferably present at the p-position.

Where the compound of formula (I) is copolymerized with the compound offormula (II), the former is usually used in a proportion of 50 to 95 mol%, and the latter 5 to 50 mol %.

Where the compound of formula (I) is copolymerized with the compound offormula (III), the former is usually used in a proportion of 50 to 95mol %, preferably 55 to 85 mol %, and the latter is usually used in aproportion of 5 to 50 mol %, preferably 15 to 45 mol %. If theproportion of the compound of formula (III) exceeds 50 mol %,disadvantages such that the resulting polymer has insufficient molecularweight tend to result. If it is less than 5 mol %, the resulting polymertends to fail to have sufficient solvent resistance as intended.

In copolymerizing the compound of formula (I) with the compound offormula (IV), the former is usually used in a proportion of 50 to 95 mol%, and the latter 5 to 50 mol %. If the proportion of the compound offormula (IV) exceeds 50 mol %, disadvantages such that the resultingpolymer has insufficient molecular weight tend to result. If it is lessthan 5 mol %, the resulting polymer tends to fail to have sufficientsolubility as intended or sufficient solvent resistance as intended.

In copolymerizing the compound of formula (I) with the compound offormula (V), the former is usually used in a proportion of 75 to 95 mol%, preferably 80 to 95 mol %, and the latter is usually used in aproportion of 5 to 25 mol %, preferably 5 to 20 mol %. If the proportionof the compound of formula (V) exceeds 25 mol %, disadvantages such thatthe resulting polymer has insufficient solubility can result. If it isless than 5 mol %, the resulting polymer tends to fail to havesufficient solvent resistance as intended.

In copolymerizing the compound of formula (I) with the compound offormula (VI), the former is usually used in a proportion of 50 to 95 mol%, preferably 60 to 95 mol %, and the latter is usually used in aproportion of 5 to 50 mol %, preferably 5 to 40 mol %. If the proportionof the compound of formula (VI) exceeds 50 mol %, disadvantages suchthat the resulting polymer has insufficient molecular weight andsolubility can result. If it is less than 5 mol %, the resulting polymertends to fail to have sufficient solvent resistance as intended.

The catalyst system which can be used in the production of thephenylene-containing polymer of the present invention contains atransition metal compound. The catalyst system essentially comprises (1)a combination of a transition metal salt and a ligand or a transitionmetal (or salt) having a ligand coordinated thereto and (2) a reducingagent. The catalyst system may further contain a salt to increase therate of polymerization.

The transition metal salt includes nickel compounds, such as nickelchloride, nickel bromide, nickel iodide, and nickel acetylacetonate;palladium compounds, such as palladium chloride, palladium bromide, andpalladium iodide; iron compounds, such as iron chloride, iron bromide,and iron iodide; and cobalt compounds, such as cobalt chloride, cobaltbromide, and cobalt iodide. Preferred among them are nickel chloride andnickel bromide.

The ligand includes triphenylphosphine, 2,2′-bipyridine,1,5-cyclooctadiene, and 1,3-bis(diphenylphosphino)propane, withtriphenylphosphine and 2,2′-bipyridine being preferred. These ligandsmay be used either individually or as a combination of two or morethereof.

The transition metal (or salt) having a ligand coordinated theretoincludes di(triphenylphosphine)nickel chloride,di(triphenylphosphine)nickel bromide, di(triphenylphosphine)nickeliodide, di(triphenylphosphine)nickel nitrate, 2,2′-bipyridinenickelchloride, 2,2′-bipyridinenickel bromide, 2,2′-bipyridinenickel iodide,2,2′-bipyridinenickel nitrate, bis(1,5-cyclooctadiene)nickel,tetrakis(triphenylphosphine)nickel, tetrakis(triphenylphosphite)nickel,and tetrakis(triphenylphosphine)palladium, withdi(triphenylphosphine)nickel chloride and 2,2′-bipyridinenickel chloridebeing preferred.

The reducing agent to be used in the catalyst system of the presentinvention includes iron, zinc, manganese, aluminum, magnesium, sodiumand calcium, with zinc and manganese being preferred. These reducingagents can be activated on contact with an acid or an organic acid.

The salt which may be used in the catalyst system includes sodiumcompounds, such as sodium fluoride, sodium chloride, sodium bromide,sodium iodide, and sodium sulfate; potassium compounds, such aspotassium fluoride, potassium chloride, potassium bromide, potassiumiodide, and potassium sulfate; and ammonium compounds, such astetraethylammonium fluoride, tetraethylammonium chloride,tetraethylammonium bromide, tetraethylammonium iodide, andtetraethylammonium sulfate. Sodium bromide, sodium iodide, potassiumbromide, tetraethylammonium bromide and tetraethylammonium iodide arepreferred of them.

The transition metal salt or transition metal (salt) having a ligandcoordinated thereto is generally used in an amount of 0.0001 to 10 mol,preferably 0.01 to 5 mol, per mole of the compound of formula (I) or amonomer mixture of the compound of formula (I) and the compoundrepresented by formulae (II) to (V) (hereinafter inclusively referred toas “the total monomer”). If the amount of the transition metal componentis less than 0.0001 mol, the polymerization reaction does not proceedsufficiently. If it exceeds 10 mol, the molecular weight is reduced.

Where a combination of the transition metal salt and the ligand is used,the ligand is usually used in an amount of 0.1 to 100 mol, preferably 1to 10 mol, per mole of the transition metal salt. If the amount of theligand is less than 0.1 mol, the catalyst activity is insufficient. Ifit is more than 100 mol, the resulting polymer is difficult to purify.

The reducing agent is usually used in an amount of 0.1 to 100 mol,preferably 1 to 10 mol, per mole of the total monomer. If the amount ofthe reducing agent is less than 0.1 mol, the polymerization reactiondoes not proceed sufficiently. If it is more than 100 mol, the resultingpolymer is difficult to purify.

In using a salt in combination with the above essential components, thesalt is usually used in an amount of 0.001 to 100 mol, preferably 0.01to 1 mol, per mole of the total monomer. If the amount is less than0.001 mol, the effect in increasing the rate of polymerization isinsufficient. If it exceeds 100 mol, the resulting polymer is difficultto purity.

Polymerization solvents which can be used in the present inventioninclude tetrahydrofuran, cyclohexanone, dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone,γ-butyrolactone, and γ-butyrolactam. Tetrahydrofuran,N,N-dimethylformamide, N,N-dimethylacetamide, and 1-methyl-2-pyrrolidoneare preferred. It is preferred for these solvents to be dried thoroughlybefore use.

The total monomer concentration in the polymerization system is usuallyfrom 1 to 100% by weight, preferably 5 to 40% by weight.

The polymerization is usually carried out at a temperature of 0 to 200°C., preferably 50 to 90° C., for a period of 0.5 to 100 hours,preferably 1 to 40 hours.

The phenylene-containing polymer obtained by the process of the presentinvention comprises not less than 50 mol % of a repeating unitrepresented by formula (VII):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a hydrogen atom, ahalogenated alkyl group or an aryl group, or a fluorenylene group; andR¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different,each represent a hydrogen atom, a halogen atom, an alkyl group, ahalogenated alkyl group, an allyl group or an aryl group, and having aweight-average molecular weight of 1,000 to 1,000,000 on polystyreneconversion.

The phenylene-containing polymer of the present invention can consistsolely of the repeating unit represented by formula (VII) (the unitcontent=100 mol %) or contain not more than 50 mol % of other repeatingunit(s) as described hereunder.

Copolymerization of the compound of formula (I) and the compound offormulae (II) to (V) gives copolymers represented by formulae (VIII) to(X):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; and R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; R⁹, R¹⁰, R¹¹, and R¹²,which may be the same or different, each represent a hydrogen atom, ahalogen atom, a hydroxy group or a monovalent organic group; and n and meach represent a mole fraction of 50 to 95 mol % and 5 to 50 mol %,respectively, making a total of 100 mol %.

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; and R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; R²¹ and R²², which may bethe same or different, each represent an alkyl group or an aryl group,provided that at least one of R²¹ and R²² is an alkyl group; R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, which may be the same or different,each represent a hydrogen atom, a halogen atom or a monovalent organicgroup; and n and 1 each represent a mole fraction of 50 to 95 mol % and5 to 50 mol %, respectively, making a total of 100 mol %.

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; and R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; R⁴¹, R⁴², R⁴³, R⁴⁴, R⁴⁵,R⁴⁶, R⁴⁷, and R⁴⁸, which may be the same or different, each represent ahydrogen atom, a halogen atom or a monovalent organic group; and n and peach represent a mole fraction of 50 to 95 mol % and 5 to 50 mol %,respectively, making a total of 100 mol %.

In formulae (VII) to (X), it is preferred that X be

(fluorenylene group).

The phenylene-containing (co)polymer according to the present inventionprovides a film-forming material. The film-forming material of thepresent invention can be obtained by a method comprising melting thephenylene-containing (co)polymer in a powder form and pressing orinjection molding the molten polymer into film or a method comprisingdissolving the phenylene-containing (co)polymer in a solvent, castingthe polymer solution on a substrate or applying the solution to asubstrate by spin coating, followed by baking to remove the solvent.

The powdered phenylene-containing (co)polymer can be melted by heatingthe polymer to a temperature higher than the softening point usually by10 to 250° C., preferably by 40 to 150° C.

Suitable solvents for dissolving the phenylene-containing (co)polymerinclude tetrahydrofuran, cyclohexanone, dimethyl sulfoxide,N,N-dimethylformamide, N,N-dimethylacetamide, 1-methyl-2-pyrrolidone,γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycoldimethyl ether, ethylene glycol methyl ethyl ether, ethylene glycolmonoethyl ether, methyl cellosolve acetate, ethyl cellosolve acetate,diethylene glycol monomethyl ether, diethylene glycol diethyl ether,diethylene glycol dimethyl ether, diethylene glycol ethyl methyl ether,diethylene glycol monoethyl ether, diethylene glycol monobutyl ether,propylene glycol methyl ether acetate, propylene glycol ethyl etheracetate, toluene, xylene, methyl ethyl ketone, methyl amyl ketone,4-hydroxyl-4-methyl-2-pentanone, ethyl 2-hydroxypropionate, methyl2-hydroxy-2-methylpropionate, ethyl 2-hydroxy-2-methylpropionate, ethylethoxyacetate, ethyl hydroxyacetate, methyl 2-hydroxy-2-methylbutanoate,methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl acetate, butylacetate, methyl lactate, ethyl lactate, chloroform, and methylenechloride. Preferred of them are cyclohexanone, N,N-dimethylacetamide,1-methyl-2-pyrrolidone, γ-butyrolactone, ethyl 3-ethoxypropionate, ethyllactate, propylene glycol monomethyl ether acetate, ethylene glycolmonoethyl ether acetate, and methyl amyl ketone.

The phenylene-containing (co)polymer is dissolved in the solvent in aconcentration of 1 to 60% by weight, preferably 5 to 40% by weight. Ifthe concentration is lower than 1% by weight, a film of sufficientthickness is hardly obtainable. If it is higher than 60% by weight, thesolution hardly spreads, failing to provide a uniform film.

If desired, additives can be incorporated into the phenylene-containingpolymer having the repeating unit of formula (VII) or represented byformulae (VIII) to (X). Suitable additives include silane couplingagents, methylol melamine, and bonding aids and crosslinking agents suchas triazene compounds.

The phenylene-containing polymers produced by the process of the presentinvention are useful as an interlayer dielectric film, a protectivefilm, a low-reflective coating, an optical waveguide material, an antireflection coating, a sealant, an alignment layer for liquid crystaldisplay, a printed circuit board material, a gas-permeable film, and thelike. They are particularly suited as an interlayer dielectric film andan optical material.

EXAMPLES

The present invention will now be illustrated in greater detail withreference to Examples, but it should be understood that the presentinvention is not limited thereto. Unless otherwise noted, all thepercents and parts are by weight. In Examples measurements andevaluation were made as follows.

1) Weight-Average Molecular Weight (Mw)

Measured by gel-permeation chromatography (GPC) on polystyreneconversion.

2) Temperature at 5% loss (Td₅)

Measured by thermogravimetry at a rate of temperature rise of 10° C./minin a nitrogen atmosphere.

3) Glass Transition Temperature (Tg)

Measured by differential scanning calorimetry at a rate of temperaturerise of 20° C./min.

4) Film-forming Properties

A polymer was dissolved in cyclohexanone (or 1-methyl-2-pyrrolidone inExample 19) at a concentration of 20%. The solution was applied to aglass substrate by spin coating and baked at 80° C. for 2 minutes, at120° C. for 2 minutes, and finally at 160° C. for 30 minutes (or 230° C.for 30 minutes in Example 19). The appearance of the resulting coat wasobserved with the naked eye.

5) Dielectric Constant

A coating film of a polymer was formed on a SUS substrate in the samemanner as described in (4) above. A gold electrode was formed thereon byvacuum deposition through a mask to prepare a specimen for measurementof relative dielectric constant. The electrostatic capacity was measuredwith an LCR meter, from which the dielectric constant ∈was obtainedthrough equation:

∈=C•d/∈₀•S

wherein ∈ is a dielectric constant; C is an electrostatic capacity; ∈₀is a unit dielectric constant in vacuo; and S is the area of the upperelectrode at 1 MHz.

6) Volume Resistivity

Measured in accordance with JIS K6911, except for using a specimenprepared by applying a polymer to a SUS substrate.

7) Organic Solvent Solubility

A powdered polymer was added to a test solvent in a concentration of20%, and the dissolution behavior at 23° C. was observed with the nakedeye.

Test solvent

NMP: 1-Methyl-2-pyrrolidone

CHN: Cyclohexanone

PGMEA: Propylene glycol 1-monomethyl ether 2-acetate

Standard of Evaluation

A . . . Completely dissolved

B . . . Partly dissolved

C . . . Not dissolved

8) Solvent Resistance

A coating film prepared in Test Example hereinafter given was immersedin a test solvent at 23° C. for 10 minutes, and any change in appearancewas observed with the naked eye.

Test Solvent

NMP: 1-methyl-2-pyrrolidone

DMSO: Dimethyl sulfoxide

PGMEA: Propylene glycol 1-monomethyl ether 2-acetate

Standard of Evaluation

A . . . No change

B . . . Peeling and swelling

C . . . Dissolution

Example 1

In a 500 ml-volume three-necked flask equipped with a tube forintroducing argon gas and a thermometer were charged 7.5 g of sodiumiodide, 1.3 g of anhydrous nickel chloride, 15.7 g oftriphenylphosphine, 45.8 g of zinc powder activated with acetic acid,and 49.2 g of 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane. Themixture was dried in vacuo for 24 hours, and the flask was filled withargon gas. In the flask was put 150 ml of dry N,N-dimethylacetamide, andthe mixture was stirred at 70° C. in an argon stream, whereupon thereaction mixture turned brown. The reaction was continued at 70° C. for20 hours. The reaction mixture was poured into a mixture of 500 ml of36% hydrochloric acid and 2000 ml of methanol, and the precipitateformed was collected.

The precipitate was suspended in chloroform and extracted with a 2Nhydrochloric acid aqueous solution. The chloroform layer was poured intomethanol, and the precipitate was collected and dried to obtain a whitepowdered polymer. The results of analysis and evaluation on theresulting polymer are shown in Table 2 below.

Examples 2 to 11

Polymers were produced in the same manner as in Example 1, except forreplacing the 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane (49.2g) with the monomer or monomers shown in Table 1 below. The results ofanalysis and evaluation on the resulting polymers are shown in Table 2.

Examples 12 and 13

Polymers were produced in the same manner as in Example 1, except forreplacing the 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane (49.2g) with the monomers shown in Table 1 below.

Ten grams of the resulting copolymer were put in a 300 ml-volumeegg-plant flask equipped with a reflux condenser and a stirrer, and 0.5g of p-toluenesulfonic acid monohydrate and 220 g of toluene were addedthereto, followed by stirring at 120° C. for 3 hours. The reactionmixture was concentrated to about 50 ml. The concentrate was poured intomethanol to re-precipitate to give a white powdered polymer having ahydroxyl group. The results of analysis and evaluation on the resultingcopolymer are shown in Table 2.

Example 14

A polymer was produced in the same manner as in Example 1, except forreplacing the 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane (49.2g) with the monomers shown in Table 1 below.

In an egg-plant flask equipped with a stirrer were charged 10.9 g ofpotassium t-butoxide and 100 ml of dimethyl sulfoxide to prepare auniform solution. To the solution was added 10 g of the resultingpolymer, followed by stirring at 80° C. for 4 hours. The reactionmixture was poured into a mixture of 250 ml of 0.5N hydrochloric acidand 500 ml of methanol. The precipitate thus formed was collected,dissolved in 100 ml of chloroform, washed twice with 2N hydrochloricacid and then once with pure water, and re-precipitated in methanol toobtain a white powdered polymer having a carboxyl group. The results ofanalysis and evaluation on the resulting polymer are shown in Table 2.

Example 15

In a 500 ml-volume three-necked flask equipped with a tube forintroducing argon gas and a thermometer were charged 7.5 g of sodiumiodide, 1.3 g of anhydrous nickel chloride, 15.7 g oftriphenylphosphine, 45.8 g of zinc powder activated with acetic acid,and 2,2-bis(4-methylsulfonyloxyphenyl)hexafluoropropane of the amountshown in Table 1. The mixture was dried in vacuo for 24 hours, and theflask was filled with argon gas. In the flask was put 150 ml of dryN,N-dimethylacetamide, and the mixture was stirred at 70° C. in an argonstream, whereupon the reaction mixture turned brown.2,4-Dichlorobenzotrifluoride in the amount shown in Table 1 was put inthe flask by means of a syringe, and the reaction was continued at 70°C. for 20 hours. The reaction mixture was poured into a mixture of 500ml of 36% hydrochloric acid and 2000 ml of methanol, and the precipitateformed was collected.

The precipitate was suspended in chloroform and extracted with a 2Nhydrochloric acid aqueous solution. The chloroform layer was poured intoacetone, and the precipitate was collected and dried to obtain a whitepowdered polymer. The results of analysis and evaluation on theresulting polymer are shown in Table 2 below.

Examples 16 to 18

Polymers were produced in the same manner as in Example 15, except forusing the monomers shown in Table 1. The results of analysis andevaluation on the resulting copolymers are shown in Table 2 below.

Example 19

In a 500 ml-volume three-necked flask equipped with a tube forintroducing argon gas and a thermometer were charged 7.5 g of sodiumiodide, 1.3 g of anhydrous nickel chloride, 15.7 g oftriphenylphosphine, 45.8 g of zinc powder activated with acetic acid,and 50.7 g of 9,9-bis(methylsulfonyloxyphenyl)fluorene. The mixture wasdried in vacuo for 24 hours, and the flask was filled with argon gas. Inthe flask was put 150 ml of dry N,N-dimethylacetamide, and the mixturewas stirred at 70° C. in an argon stream, whereupon the reaction mixtureturned brown. The reaction was continued at 70° C. for 20 hours. Thereaction mixture was poured into a mixture of 500 ml of 36% hydrochloricacid and 2000 ml of methanol, and the precipitate formed was collected.

The precipitate was suspended in chloroform and extracted with a 2Nhydrochloric acid aqueous solution. The chloroform layer was poured intoacetone, and the precipitate was collected and dried to obtain a whitepowdered polymer. The results of analysis and evaluation on theresulting polymer are shown in Table 2 below.

Example 20

A polymer was produced in the same manner as in Example 19, except forreplacing the 9,9-bis(methylsulfonyloxyphenyl)fluorene (50.7 g) with themonomers shown in Table 1. The results of analysis and evaluation on theresulting copolymers are shown in Table 2 below.

TABLE 1 Monomer(s) Amount Amount Example (g) (g) No. Kind (mol %) Kind(mol %)  1 2,2-bis(4-methylsulfonyloxy- 49.2 — —phenyl)hexafluoropropane (100)  2 bis(4-methylsulfonyloxyphenyl)- 50.0 —— trifluoromethylphenylmethane (100)  3 bis(3-fluoro-4-methylsulfonyl-54.4 — — oxyphenyl)diphenylmethane (100)  4 2,2-bis(4-methylsulfonyloxy-39.4 2,2-bis(4-methylsulfonyloxy- 7.68 phenyl)hexafluoropropane (80)phenyl)propane (20)  5 2,2-bis(4-methylsulfonyloxy- 39.4bis(4-methylsulfonyloxyphenyl)- 7.12 phenyl)hexafluoropropane (80)methane (20)  6 2,2-bis(4-methylsulfonyloxy- 29.5bis(3,3′-allyl-4,4′-(p-fluoro- 23.3 phenyl)hexafluoropropane (60)phenyl)sulfonyloxy)biphenyl (40)  7 2,2-bis(4-methylsulfonyloxy- 39.42,4-dichlorobenzophenone 5.02 phenyl)hexafluoropropane (80) (20)  82,2-bis(4-methylsulfonyloxy- 39.4 2,4-dichlorobenzyl alcohol 3.54phenyl)hexafluoropropane (80) (20)  9 2,2-bis(4-methylsulfonyloxy- 39.43,5-dichlorobenzyl alcohol 3.54 phenyl)hexafluoropropane (80) (20) 102,2-bis(4-methylsulfonyloxy- 29.5 3,5-dichlorobenzyl alcohol 7.08phenyl)hexafluoropropane (60) (40) 11 2,2-bis(4-methylsulfonyloxy- 41.83,6-dichlorophthalic acid 3.26 phenyl)hexafluoropropane (80) anhydride(20) 12 2,2-bis(4-methylsulfonyloxy- 39.4 3,5-dichlorophenyl-t-butoxy-5.26 phenyl)hexafluoropropane (60) carbonyl (40) 132,2-bis(4-methylsulfonyloxy- 29.5 3,5-dichlorophenyl-t-butoxy- 10.5phenyl)hexafluoropropane (80) carbonyl (20) 142,2-bis(4-methylsulfonyloxy- 39.4 methyl 3,5-dichlorobenzoate 4.10phenyl)hexafluoropropane (80) (20) 15 2,2-bis(4-methylsulfonyloxy- 29.52,4-dichlorobenzotrifluoride 8.60 phenyl)hexafluoropropane (60) (40) 162,2-bis(4-methylsulfonyloxy- 39.4 2,4-dichloroanisole 3.54phenyl)hexafluoropropane (80) (20) 17 9,9-bis(4-methylsulfonyloxy- 42.62,4-dichlorobenzotrifluoride 3.44 phenyl)fluorene (80) (20) 189,9-bis(4-methylsulfonyloxy- 25.4 2,4-dichlorobenzotrifluoride 11.0phenyl)fluorene (50) (50) 19 9,9-bis(4-methylsulfonyloxy- 50.7 — —phenyl)fluorene (100) 20 9,9-bis(4-methylsulfonyloxy- 30.4bis(4-methylsulfonyloxyphenyl)- 23.3 phenyl)fluorene (60)diphenylmethane (40)

TABLE 2 Example Td₅ Tg Solubility No. Mw (° C.) (° C.) ε NMP cHN PGMEA 1 34700 533 251 2.2 A A A  2 16600 511 266 2.3 A A A  3  9600 549 2342.4 A A A  4 25800 505 239 2.3 A A A  5 25200 501 230 2.3 A A A  6 20800470 * 2.3 A A A  7 28100 521 186 2.4 A A A  8 14400 514 198 2.3 A A A  915200 502 210 2.3 A A A 10 11800 493 205 2.4 A A A 11 43300 517 230 2.3A A A 12 20500 512 242 2.3 A A A 13 25900 510 235 2.4 A A A 14 12500 511233 2.3 A A A 15 20000 517 215 2.2 A A A 16 14400 462 183 2.3 A A A 1723400 567 >350   2.4 A A C 18 25200 553 >350   2.4 A A C 19 21800576 >350   2.4 A B C 20 20100 563 >350   2.4 A A C Note: * undetected.

In all of Examples 1 to 20 the polymer had a volume resistivity of 10¹⁶Ω.cm² or higher and showed satisfactory film-forming properties.

9) IR Analysis

The polymers obtained in Examples 1 to 20 were analyzed by IR absorptionspectrum by KBr tablet method. The results obtained are shown in FIGS. 1through 20.

Test Example 1

A hundred parts of the polymer obtained in Example 6, parts of2,5-dimethyl-2,5-di(t-butylperoxy)hexyn-3, and 1 part of3-glycidyloxypropyltrimethoxysilane were dissolved in 300 parts ofpropylene glycol 1-monomethyl ether 2-acetate. The resulting polymercomposition was applied by spin coating onto a glass substrate to athickness of 3 μm and baked at 80° C. and then 120° C. for 2 minuteseach and finally baked in a nitrogen stream at 250° C. for 30 minutes toobtain a transparent coating film. The coating film was evaluated toobtain the results shown in Table 3 below.

Test Example 2

A hundred parts of the polymer obtained in Example 8, 40 parts of Cymel300 (produced by Mitsui-Cytec, Ltd.), and 1 part of3-glycidyloxypropyltrimethoxysilane were dissolved in 300 parts ofpropylene glycol 1-monomethyl ether 2-acetate. The resulting polymercomposition was applied by spin coating onto a glass substrate to athickness of 3 μm and baked at 80° C. and 120° C. for 2 minutes each andfinally at 230° C. for 30 minutes to obtain a transparent coating film.The coating film was evaluated to obtain the results shown in Table 3.

Test Examples 3 to 8

A coating film was prepared in the same manner as in Test Example 2,except for using the polymer shown in Table 3. The results of evaluationare shown in Table 3.

TABLE 3 Test Example Dielectric Solvent Resistance No. Polymer ConstantNMP DMSO PGMEA 1 Ex. 6  2.4 A A A 2 Ex. 8  2.5 A A A 3 Ex. 9  2.5 A A A4 Ex. 10 2.5 A A A 5 Ex. 11 2.5 A A A 6 Ex. 12 2.5 A A A 7 Ex. 13 2.5 AA A 8 Ex. 14 2.5 A A A

INDUSTRIAL APPLICABILITY

In the present invention, a monomer prepared by sulfonating aneconomically available bisphenol compound is polymerized in the presenceof a transition metal catalyst. There is produced through an economicalprocess a polymer satisfying the requirements of heat resistance, lowdielectric properties, and processability. Further, the polymer providesa highly transparent film.

Where the above-mentioned monomer is copolymerized with a dihalo- orbissulfonate compound having a reactive functional group or a precursorthereof, copolymers exhibiting solvent resistance and adhesion inaddition to the above characteristics can be obtained.

What is claimed is:
 1. A process for producing a phenylene-containingpolymer comprising polymerizing a monomer comprising not less than 50mol % of a compound represented by formula (I):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; R¹, R², R³,R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; and Z represents an alkylgroup, a halogenated alkyl group or an aryl group, in the presence of acatalyst system containing a transition metal compound.
 2. The processaccording to claim 1, wherein said monomer comprises 60 mol % or more ofthe compound represented by formula (I).
 3. The process according toclaim 1, wherein said monomer comprises 80 mol % or more of the compoundrepresented by formula (I).
 4. The process according to claim 1, whereinsaid monomer consists solely of the compound represented by formula (I).5. The process according to claim 1, wherein said monomer comprises twoor more kinds of the compound represented by formula (I).
 6. The processaccording to claim 1, wherein said monomer comprises 50 to 95 mol % ofthe compound represented by formula (I) and 5 to 50 mol % of a compoundrepresented by formula (II):

wherein R⁹, R¹⁰, R¹¹, and R¹², which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, a hydroxy group or amonovalent organic group; and R³¹ represents a halogen atom or a groupof formula: —OSO₂Z, wherein Z represents an alkyl group, a halogenatedalkyl group or an aryl group.
 7. The process according to claim 6,wherein at least one of R⁹, R¹⁰, R¹¹, and R¹² in formula (II) is amonovalent reactive group or a precursor thereof.
 8. The processaccording to claim 7, wherein said monovalent reactive group or aprecursor thereof is selected from the group consisting of a hydroxylgroup, a carboxyl group, an allyl group, and an alkoxycarbonyloxy group.9. The process according to claim 1, wherein said monomer comprises 50to 95 mol % of the compound represented by formula (I) and 5 to 50 mol %of a compound represented by formula (III):

wherein R⁹, R¹⁰, R¹¹, and R¹², which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, a hydroxyl group or amonovalent organic group; and R³² represents a halogen atom or a groupof formula: —OSO₂Z, wherein Z represents an alkyl group, a halogenatedalkyl group or an aryl group.
 10. The process according to claim 9,wherein at least one of R⁹, R¹⁰, R¹¹, and R¹² in formula (III) is amonovalent reactive group or a precursor thereof.
 11. The processaccording to claim 10, wherein said monovalent reactive group or aprecursor thereof is selected from the group consisting of a hydroxylgroup, a carboxyl group, an allyl group, and an alkoxycarbonyloxy group.12. The process according to claim 1, wherein said monomer comprises 50to 95 mol % of the compound represented by formula (I) and 5 to 50 mol %of a compound represented by formula (IV):

wherein R²¹ and R²², which may be the same or different, each representan alkyl group or an aryl group, provided that at least one of R²¹ andR²² is an alkyl group; R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, whichmay be the same or different, each represent a hydrogen atom, a halogenatom or a monovalent organic group; and R³³ represents a halogen atom ora group of formula: —OSO₂Z, wherein Z represents an alkyl group, ahalogenated alkyl group or an aryl group.
 13. The process according toclaim 1, wherein said monomer comprises 75 to 95 mol % of the compoundrepresented by formula (I) and 5 to 25 mol % of a compound representedby formula (V):

wherein R¹³, R¹⁴, R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, which may be thesame or different, each represent a hydrogen atom, a halogen atom, analkyl group, a halogenated alkyl group or an aryl group; and R³⁴represents a group of formula: —OSO₂Z, wherein Z represents an alkylgroup, a halogenated alkyl group or an aryl group.
 14. The processaccording to claim 1, wherein said monomer comprises 50 to 95 mol % ofthe compound represented by formula (I) and 5 to 50 mol % of a compoundrepresented by formula (VI):

wherein R²³, R²⁴, R²⁵, R²⁶, R²⁷, R²⁸, R²⁹, and R³⁰ each represent ahydrogen atom or an allyl group, provided that at least one of R²³ toR³⁰ is an allyl group; and R³⁴ represents a halogen atom or a group offormula: —OSO₂Z, wherein Z represents an alkyl group, a halogenatedalkyl group or an aryl group.
 15. The process according to claim 1,wherein X is a group represented by formula: —C(CF₃)₂—.
 16. The processaccording to claim 1, wherein X is a group represented by formula:


17. The process according to claim 1, wherein X is a fluorenylene grouprepresented by formula:


18. A film-forming material comprising a phenylene-containing polymercomprising a repeating unit represented by:

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a hydrogen atom, ahalogenated alkyl group or an aryl group, or a fluorenylene group; andR¹, R², R³, R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different,each represent a hydrogen atom, a halogen atom, an alkyl group, ahalogenated alkyl group, an allyl group or an aryl group; n represents amole fraction of 50 mol % or more; and the phenylene-containing polymerhas a weight-average molecular weight of 1,000 to 1,000,000 onpolystyrene conversion.
 19. The film-forming material according to claim18, wherein X is a fluorenylene group represented by formula:


20. The film-forming material according to claim 18, wherein X is agroup represented by formula:


21. The film-forming material according to claim 18, wherein saidpolymer is represented by formula (VIII):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; and R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; R⁹, R¹⁰, R¹¹, and R¹²,which may be the same or different, each represent a hydrogen atom, ahalogen atom, a hydroxy group, or a monovalent organic group; and n andm each represent a mole fraction of 50 to 95 mol % and 5 to 50 mol %,respectively, making a total of 100 mol %, and has a weight-averagemolecular weight of 1,000 to 1,000,000 on polystyrene conversion. 22.The film-forming material according to claim 21, wherein at least one ofR⁹, R¹⁰, R¹¹, and R¹² is a monovalent reactive group or a precursorthereof.
 23. The film-forming material according to claim 22, whereinsaid monovalent reactive group or a precursor thereof is selected fromthe group consisting of a hydroxyl group, a carboxyl group, an allylgroup, and an alkoxycarbonyloxy group.
 24. The film-forming materialaccording to claim 18, wherein said polymer is represented by formula(IX):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; and R¹, R²,R³, R⁴, R⁵, R⁶, R⁷, and R⁸which may be the same or different, eachrepresent a hydrogen atom, a halogen atom, an alkyl group, a halogenatedalkyl group, an allyl group or an aryl group; R²¹ and R²² which may bethe same or different, each represent an alkyl group or an aryl group,provided that at least one of R²¹ and R²² is an alkyl group; R¹³, R¹⁴,R¹⁵, R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, which may be the same or different,each represent a hydrogen atom, a halogen atom or a monovalent organicgroup; and n and 1 each represent a mole fraction of 50 to 95 mol % and5 to 50 mol %, respectively, making a total of 100 mol %, and has aweight-average molecular weight of 1,000 to 1,000,000 on polystyreneconversion.
 25. The film-forming material according to claim 18, whereinsaid polymer is represented by formula (X):

wherein X represents a group of formula: —CYY′—, wherein Y and Y′, whichmay be the same or different, each represent a halogenated alkyl group,a hydrogen atom or an aryl group, or a fluorenylene group; and R⁴¹, R⁴²,R⁴³, R⁴⁴, R⁴⁵, R⁴⁶, R⁴⁷, and R⁴⁸, which may be the same or different,each represent a hydrogen atom, a halogen atom, an alkyl group, ahalogenated alkyl group, an allyl group or an aryl group; R¹³, R¹⁴, R¹⁵,R¹⁶, R¹⁷, R¹⁸, R¹⁹, and R²⁰, which may be the same or different, eachrepresent a hydrogen atom, a halogen atom or a monovalent organic group;and n and p each represent a mole fraction of 50 to 95 mol % and 5 to 50mol %, respectively, making a total of 100 mol %, and has aweight-average molecular weight of 1,000 to 1,000,000 on polystyreneconversion.
 26. An electrically insulating material comprising thefilm-forming material according to claim
 18. 27. An optical materialcomprising the film-forming material according to claim 18.